Manganese activated zinc barium silicate phosphor



Feb. 6, 1951 J. T. ANDERSON ET AL 2, ,8

MANGANESE ACTIVATED ZINC BARIUM SILICATE PHOSPHOR Filed April 1, 1949 ZnO YAVAVAVAVA AYAYAYAVAYAVA @wmu James T Anderson, Robert S. Wel'ls,

b MD

Their Attorneg.

Patented Feb. 6, 19 51 MANGANESE ACTIVATED znio Benton" H v SILICATE PHOSPHOR j James .T. Anderson and Robert S...Wells,. Rugby,

vEngland, .assignors ;to General pany, a corporation of ew York Application April 1, 1949, Serial No. l InGreat Britain April 9, 1948 Claims. icrztwataea This invention relates to improvements in luminescence from blue to red. For luminescence falling in the middle or this range a large number of materials are available, but ateach end of the ;range the choice becomes more especially -at;;tl 1 e red end of the range. Known materials, which have a red luminescence when excited by short ultraiolet radiation around 2537 A are zinc-beryllium-silicate, cadmium borate, and calcium-cerium-manganese phosphate; of these, calcium-cerium-manganese phosphate gives the deepest red luminescence, with the peak of its emission curve at about 6500 A, compared with that of cadmium borate at 6200 A. It might be thought that the difference in appearance between materials peaking at 6200 A. and 6500 A. would be small; this is, however, not the case since if cadmium borate is compared directly with calcium-cerium-manganese phosphate it appears tobe orange-red to the eye.

We have evolved a material emitting a deepred luminescence with the peak of its emission cum e at about 6750 A. when excited by ultraviolet radiation around 2537 A. The material is also capable of being excited by cathode rays, and

to some extent by ultra-violet radiation around 3650 A. e

A luminescent material according to the invention comprises zinc-barium silicate of general formula 2ZnO.BaO.rSiO2 (where a: has a value between 1.7 and 12) activated with manganese. The materials may conveniently be designated by reference to the accompanying ternary diagram in which the percentages are calculated in molecules (rather than in the usual way, in weights) of the three components.

Luminescent materials according to the invention thus have. referring to the diagram, molecular compositions which are represented by that portion of the limb BE lying between F and a. where Fjj epresents 2ZnQ.BaO.l2SiOz and 0 represents 2ZnO.BaO.1.7SiO2 and show a sun-i form deep red luminescence when activated with manganese.

' .nmaterialorthe compesitionz'znon oacsioz showedalmostno fluorescence.

If. large proportionslol 5102. are added, a, i a move is .madev down, the line EB towards the,

point P there is .a diminution in the intensityof fluorescence, which lsrelat'ively small, until 9. composition. of.2ZnO.-B aO .6S iO2 'isi'reached; after more-apparent, land'aiterlthe point l v .2Znf9iBaD:l2SiOzr.::.5Q s has been passed, the fluorescence becomes very weak, finally extinguishing at B% S102.

If more ZnO than 2Zn-O.Ba0 is used, there is a dilution of the red 2ZnO.BaO.:cSiOz material with green fluorescent zinc silicate, which becomes more apparent as the ZnO ratio is increased, particularly since the green of the zinc silicate is more visible to the eye than the red.

Conversely if the Ba'O proportion is increased there is a dilution of the red fluorescent material with non-fluorescent barium silicate.

For the best results a: should be between 1.7 and 6, and preferably be closer to 1.7 than 6, for example 2.

' The manganese is preferably added as MnClzAHzO in solution in water or water ethyl alcohol mix ture, but we do not exclude the use of other suitable manganese compounds. The quantity is preferably 5% of MnClzAHzO per mixed dry ingredients, but may be varied between 2 /2721 and 10% without much depreciation of the phosphor. Beyond these limits there is appreciable decrease in fluorescent brightness.

The preferred raw materials from which the luminescent materials of the invention are prepared are BaCOa of analar purity, ZnO of Analar purity, and a suitably fine, reactive form of silica, such as is known to be required which the diluting effect. of ,the silica becomes.

by these versed in the art of making fluorescent materials-: fghe ZnO, and BaCOa can be replaced bysuitablefcompound's which during the subse- 2,540,804 1 j a r 3 quent firing process to which the mixed materials are subjected would make ZnO, and BaO available for reaction with the SiOz.

The MnClgAHzO is of Analar purity.

The desired quantities of the dry ingredients are intimately mixed, the correct amount of manganese chloride solution is added, and mixed therewithLQzmd the mixture dried in the oven, and reground and thoroughly mixed.

The mixture is fired in suitable crucibles, e. g., silica, at a temperature of 1100 Chi-150 C. in periods of /2 to 2 hours at a time, according to quantity, until maximum brilliance is attained.

This may take 5 hours or more. Some variation in the firing temperature is permissible, but the material should not be melted; the reaction is slow below10. 00 c.

A preferred composition'may be prepared by mixing the following quantities of the ingredients:

BaCO3, 19 .75grams (approx. 1 mollBaO) ZnO, 16.30 grams (approx. 2 mol ZnO) SiOz (containing 5% water), 14.15 grams (approx.

22 mol anhydrous SiOz') Adding the MnClAHO solution andtreating as indicated above.

What we claim as new and desire to secure by MI1C12.4H2O in an amount from 2%% to 10% f the mixed dry ingredients of the luminescent material.

'3. 'A zinc-barium silicate luminescent material having the general formula 2ZnO.BaO.a:Si0z where a: has a value of approximately 2, the lumilescent material being activated by a quantity of manganese equal to that obtained by utilizing MnClz.4I-Iz0 in an amount from 2 /2% to 10% of the mixed dry ingredients of the luminescent material. l

' 4. The method of preparing a barium-zinc silicate luminescent material which comprises mixing barium carbonate, zinc oxide and silicon dioxide (containing approximately water) in relative weights of approximately 19.75, 16.30 and 14.15 adding 2 /2 to %,by weight of the mixed ingredients of MnClz.4HzO and firing the mixture at a temperature of 1050 C. to 1150 C. until maximum brilliance is obtained.

' 5. The method of preparing a manganese acti- 'vated luminescent material having the general formula 2ZnO.BaO..rSiOz where a: has a value between 1.7 and 12 which comprises mixing pow-v dered ZnO, S102, and a BaO yielding compound in the ratio required to produce a material having said formula, adding MnClzAHzO in a quantity of 2 to 10% by weight of the powdered mix-" ture and firing the product at 1050 C. to 1150" C."

JAMES T. ANDERSONQ ROBERT s. WELLS. 1

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,108,683 Leverenz Feb. 15, 1938 2,118,091 Leverenz May 24, 1938:

Headrick Aug. 8, 1939 

1. A ZINC-BARIUM SILICATE LUMINESCENT MATERIAL HAVING THE GENERAL FORMULA 2ZNO.BAO.XSIO2 WHERE X HAS A VALUE BETWEEN 197 AND 12, THE LUMINESCENT MATERIAL BEING ACTIVATED BY A QUANTITY OF MANGANESE EQUAL TO THAT OBTAINED BY UTILIZING MNCL2.4H2O IN AN AMOUNT FROM 2 1/2% TO 10% OF THE MIXED DRY INGREDIENTS OF THE LUMINESCENT MATERIAL. 